Polyolefins blended with amineepoxide condensate



United States Patent 3,294,864 POLYOLEFINS BLENDED WITH AMINE- EPOXIDECONDENSATE Gabriel Karoly, Elizabeth, Allen Noshay, Fords, Fritz B.Marktschelfel, Berkeley Heights, and Alhin F. Turbak, New Providence,N.J., assignors to Essa Research and Engineering Company, a corporationof Delaware No Drawing. Filed Oct. 5, 1962, Ser. No. 228,754 4 Claims.(Cl. 260836) This invention relates to a process for treating alphaolefin polymers to render them dyeable.

Poly alpha olefin polymers have found increasing interest as textilematerials because of their desirable properties of strength and lowcost. One of the more diflicult problems encountered, however, has beenconcerned with the relative ease of dyeing and relative quality of dyedfilaments in view of the inertness of a hydrocarbon polymer. Although apoly alpha olefin material, such as polypropylene, can be dyed, itsfastness to typical textile environments has been inadequate.

It has now been found that the addition of certain condensation productsof a polyepoxide and an amine compound to the polymer prior to spinningin amounts that produce considerable improvements in dyecharacteristics, permits satisfactory spinning without extensive loss infiber tensile properties while providing a readily dyeable textilefilament with unusually improved fastness properties. One to twentyweight percent of condensate may be blended with 99 to 80 weight percentof polymer, although it is preferred to use 3 to 12 weight percent ofcondensate with 97 to 88% of polymer.

The preparation of textile filaments by melt spinning of poly alphaolefins places rather stringent requirements upon materials that may beblended with these polymers. High spinning temperatures and prolongedheating of polymers at those temperatures require that blended materialshave satisfactory heat stability. It has been found that blending ofsuch heat stable products of the condensate of polyepoxy compounds andamine compounds is easily accomplished when these products are linearand when the nitrogen in these condensed compounds is present in thetertiary amineform. When the products are crosslinked totally or insubstantial pa-rt,--they do not blend satisfactorily with the textilefilament polymer for good spinning. In addition, when a substantialnumber of secondary amine groups are present in the condensation prodnotblending agent, severe degradation of the blend is observed during meltspinning. Thus primary amines are not suitable in this invention sincewhen they are reacted with a polyepoxy compound, a product is producedwhich contains secondary amine groups.

When poly alpha olefin filaments containing the condensation products ofthis invention are subjected to typical dyeing procedures, it is foundthat the dye uptake is improved and more importantly, the resistance ofthe dyed product to fading in light, in washing, and in dry cleaning isgreatly improved.

The products of this invention may be made by preparing a solution of anepoxide compound in a convenient solvent such as ethyl alcohol, propylalcohol, butyl alcohol, methyl ethyl ketone, methyl butyl ketones,cyclohexanone, cyclopentanone, benzene, toluene or xylene and thenslowly mixing with a compatible solution of the amine compound at atemperature between 2060 C. The solution may then be heated, forexample, to reflux for 1-10 hours, after which time the solvent may beremoved by distiilation, leaving in the case of resinous products as anexample, a syrupy product. This can then be further heated at about120140 C. until the condensation is substantially completed. The viscousproduct is then poured from the reactor or flask and solidifies on3,294,864 Patented Dec. 27, 1966 ice cooling to ambient temperatures. Todetermine the requirement of linearity (substantially not crosslinked),the solidified product is tested for alcohol solubility. A positive testindicates linearity and compatibility with polyolefin product. Thecondensate product may then be broken up and blended with the poly alphaolefin by the well known methods of milling, Banbury mixing, powderblending and solution blending. The blends may then be subjected to wellknown melt spinning techniques to produce readily dyeable monoandmultifilament yarn. These blends may also be wet or dry spun as well.Prior to dyeing, these yarns may be drawn, twisted, plied and knitted orwoven into various textile products. In addition, the blended materialmay instead be extruded in the form of films and foils.

The polymers treated by the process of the invention are alphamonoolefin homopolymers and copolymers. The alpha olefin homopoly-mercan be prepared by any known process, such as :the so-called Zieglerprocess, see for example Belgian Patent 533,362 and Belgian Patent538,782. Examples of homopolymers within the scope of the inventioninclude polyethylene, polypropylene and poly 1- butene. Polymers orcopolymers of branched chain alpha olefins where the branching occurs nocloser than the 3rd carbon atom can also be employed, such as poly4-methyll-pentene, poly 4,4-dimethyl-l-pentene and polyB-methyll-butene. In general, the homopolymers are prepared from alphaolefins having from 2 to 12 carbon atoms. The copolymers employed in theprocess of the invention include copolymers of two different alphaolefins such as ethylene, propylene copolymers; ethylene, l-hexenecopolymers; and alpha olefin, aromatic olefin copolymers containing from1 to 15% by weight of an aromatic olefin, such as for example copolymersof styrene and 4- methyl-l-pentene. Also, blends of one or more of thepreviously mentioned polymers can be employed. The polymers andcopolymers employed in the invention have molecular weights ranging from100,000 to 1,000,000. The preferred polymers and copolymers of theinvention are those prepared by the use of alkyl metal catalysts. Mostpreferred is polypropylene. Catalysts which are useful in this processare mixtures of reducible heavy transition metal compounds and reducingmetal containing .substances, or mixtures of partially reduced heavytransition metal compounds and organo metallic activators. Examples ofthese 'catalysts are TiCl +AlEt and TiCl +AlEt The catalysts used forpreparing the preferred polymers employed in the instant process arethose catalysts given on page 6, line 20 to page 10, line 21 ofcopending application Serial No. 831,210, filed August 3, 1959, nowabandoned.

The polyepoxides suitable for use in this invention include thoseorganic compounds which contain two or more epoxide groups (oxiranerings) and 4 or more carbon atoms.

Thus, one class of these materials which may be used are diepoxidecompounds such as vinylcyclohexene dioxide, butadiene diepoxide and Epon828, the diglycidyl ether of Bisphenol A.

Also suitable are polye-poxidized homopolymers or copolymers ofbutadiene. These are prepared by first p0.- lymerizing butadiene aloneor in conjunction with materials copolymerizable therewith such asstyrene. Various methods of polymerization, such as sodiumpolymerization, emulsion polymerization, and the like, are known in theart and any of these methods may be used. These polymers are thentreated with an oxidizing material. These include air, oxygen, and H 0alone or in the presence of peracetic or performic acid. It is furtherdesirable to treat the polymers with hydrogen to reduce some of theirunsaturation. This may be done either before or after the epoxidationstep. A preferred polybutadiene oxidized with H is sold as Oxiron, Otherpolyepoxy compounds may also be used such as Epon 1031 which has thefollowing structure:

The amino compounds suitable for use in this invention are C -Cpreferably C C alkyl, aryl, or aralkyl compounds having at least onesecondary amine group attached thereto. Secondary monoarnines, orsecondary polyamines are useful in this invention.

Examples of secondary monoairnines are diethylamine, diphenylamiue andpiperidine. Preferred is piperidine. Piperazine is an example of apreferred polyamine.

The reaction product of the polyepoxide and amino compound is acondensate which will range in consistency between liquid and solid.This condensate is blended with a poly alpha olefin and extruded or spuninto sheets, films, foils or preferably fibers. These are then treatedwith one or more dyes in aqueous media according to standard techniquesknown in the art.

In general the aqueous dye baths employed contain from 0.1 to 10 weightpercent dye based on the weight of fiber. The temperature of dyeing andthe time ofimmersion depends on the proportion of polymer and condensatein the blend, the particular polymer and condensate employed, the typeand concentration of dye employed, and the intensity of color desired,These parameters can easily be determined by routine experimentation forany particular modified polymer-dye combination. The temperature ofdyeing is not critical and can range from 25 to 120 C. although the dyebath is usually maintained at the boiling point.

The classes of dyes suitable for use in this invention include not onlydispersed dyes but also acid dyes such as Anthraquinone Blue SKY, andpremetallized dyes such as Neolau Yellow GR, After the fiber or fabricmade from the polymer blend has been immersed in the dye bath for asuitable period of time, it is removed, scoured, Washed with water, anddried.

The invention will be better understood from the fol lowing examples.

Example I A vinylcyclohexene dioxide-piperazine condensate was preparedspecifically as follows: 135 g. of vinylcyclohexene dioxide wasdissolved in 100 ml. of absolute ethyl alcohol and added over a periodof 90 minutes at 80 C. to a stirred solution of 86 g. piperazine in 150ml. of absolute alcohol. After 4 hours of refluxing, the alcohol wasstripped off and the molten condensate poured into a dish. Thecondensate contained 10.12 weight percent nitrogen.

Example 2 A vinylcyclohexene dioxide-hex'amethylene diamine condensatewas prepared specifically as follows: 350 g. (2.5 moles) ofvinylcyclohexene dioxide was dissolved in 250 ml. of absolute ethylalcohol, and added over 90 minutes, between 70-80 C., under vigorousstirring to 116 g. (1 mole) of hexamethylene diamine dissolved in 100ml. absolute alcohol. The mixture was refluxed at 82 C. for 8 hours,then the alcohol was stripped off and the molten condensate poured intoa dish. The condensate contained about nitrogen and was fully soluble inalcohol thereby indicating its non-crosslinked nature.

Example 3 Condensates as prepared in Examples 1 and 2 were blended withpolypropylene prepared by standard methods at low pressure. The polymerhad an inherent viscosity of 2.1. These blends were then melt spun intofibers and treated with dyes as shown in Table I following:

Prernetallized Dye Dispersed Dye Moderate-High.

Moderate-High. Fair-Moderate High.

Fastness:

U.V. Light No break after 20- No or slight break 30 hours in the afterhours in Fadeometer. the Fadeometer. Washing High e High. Dry CleaningHigh 8 (1) Piperazine-vinylcyelohexene dioxide condensate as prepared inExample 1.

(2) Hexamethylene diamine-vinylcyclohexene dioxide condensate asprepared in Example 2.

Anthraquinone Blue SKY.

b Sevron Red L.

G Neolan Yellow GR.

d Latyl Yellow iRL.

* Acid and prernetallized dyes.

The results recorded in Table I supra serve to espe cially point up thesignificance of the invention. In Compound (1) thepiperazine-vinylcyclohexene dioxide condensate is linear and thenitrogens are substantially all tertiary. The spinning stability is highas shown by the high tenacity of 4.39 g./denier and the modestelongation of 26.8%. In Compound 2, the nitrogens of the linearcondensate are largely secondary and the resultant tenacity is low (0.88g./den.) and the elongation is high (113%) which is typical of a.degraded unstable polymer blend. The dye absorption and the fastnessimprovements are good for both but the latter fiber is not commerciallysatisfactory.

Example 4 To a flask containing 34 g. of piperidine in 200 cc. oftetrahydrofuran at reflux was added 20 g. of Epon 1031, dissolved in cc.of tetrahydrofuran. The addition was dropwise over a 1 hour period withvigorous stirring. The reaction was then stirred for an additional 3hours. After standing overnight the tetrahydrofurau was stripped oifunder vacuum and the viscous residue was dissolved in 200 cc. ofbenzene. The product was precipitated with 600 cc. of heptane which wasadded to the stirred benzene solution. The excess liquor was then pouredoff and the precipitate was hardened in 400 cc. more heptane. The solidobtained on evaporation of solvent was crushed and the powder furtherdried to give .a light yellow powder having 5.2% nitrogen.

This product was blended at 6% by weight in a polypropylene powder andspun into fibers. It should be noted that a polypropylene blend withEpon 1031 without amine treatment did not spin satisfactorily under thesame conditions.

The fibers obtained from the blend had good tenacity and good dyeabilitywith acid and dispersed dyes, and exhibited good light fastness for 1215hours in Fadeometer exposure. Typical acid dyes used are Du Pont BlueSKY and Du Pont Rubine R.

Example 5 To a one liter flask was added 8.5 g. of pi-peridine (0.1mole) dissolved in 300 cc. of tetrahydrofuran. The liquor was heated toreflux and 17.7 g. of Oxiron 2000 (0.1 mole equivalent of oxirane),which is an epoxidized polybutadiene, was dissolved in 100 cc. oftetrahydrofuran and dropped in over a one hour period. The mixture wasstirred and heated for another hour. During the addition the mixturechanged from colorless to a pink color.

The mixture was added to isopropanol and some tacky solid separated. Theupper liquor was evaporated and finally flashed free of solvent at 7080C. and 0.2 mm. pressure leaving a reddish polymeric residue. Whenblended with polypropylene at 5 to concentration the fibers obtained hadincreasedaffinity for acid dyes and satisfactory tensile properties.

Example 6 The preparation described in Example 2 was repeated with theexception that the heating was extended an additional 16 hours to atotal of 24 hours. The recovered resin was now substantiallycrosslinked. It was insoluble in alcohol and could not be satisfactorilyblended with polypropylene.

From the above examples it can be seen that the blended polymer asprepared by this invention is spinnable and can be dyed to produce astable, fade resistant product with satisfactory tenacity andelongation.

This invention has been described in connection with certain specificembodiments thereof; however, it should be understood that these are byway of example rather than by way of limitation, and it is not intendedthat the invention be restricted thereby.

What is claimed is:

1. A spinnable composition of matter comprising a blend of 80-99 weightpercent of a C C poly alpha monolefin with 1 weight percent of a linearcondensate consisting essentially .of the reaction product ofvinylcyclohexene dioxide and a secondary polyamine compound.

2. The composition of claim 1 wherein the poly alpha monolefin ispolypropylene.

3. The composition of claim 2 wherein the amine is piperazine, andwherein 123 weight percent of the condensate is used.

4. A method for improving the dyeability of a spinnable C C poly alphamonolefin which comprises blending -99 weight percent of the poly alphamonolefin with 20-1 weight percent of a linear condensate consistingessentially of the reaction of vinylcyclohexene dioxide and a secondarypolya-mine compound.

References Cited by the Examiner UNITED STATES PATENTS 2,917,469 12/1959 Phillips et al 2602 2,921,037 1/ 1960 Andres et al 2602 2,948,6888/1960 Bender et a1 260-2 3,013,998 12/1961 Battaglioli 260836 3,051,6648/1962 Turner 2602 3,098,697 7/ 1963 Cappuccio et al. 260836 XR3,215,487 11/1965 Cappnccio et al. 855

MURRAY TILLMAN, Primary Examiner.

WILLIAM H. SHORT, Examiner.

I. W. SANNER, G. F. LESMES, Assistant Examiners.

1. A SPINNABLE COMPOSITION OF MATTER COMPRISING A BLEND OF 80-99 WEIGHTPERCENT OF A C2-C12 POLY ALPHA MONOLEFIN WITH 20-1 WEIGHT PERCENT OF ALINEAR CONDENSATE CONSISTING ESSENTIALLY OF THE REACTION PRODUCT OFVINYLCYCLOHEXENE DIOXIDE AND A SECONDARY POLYAMINE COM:POUND.